Aqueous lubricants containing siloxane-polyoxyalkylene compositions



US. Cl. 25246.3 12 Claims ABSTRACT OF THE DISCLOSURE The method oflubricating metal surfaces by applying an aqueoussiloxane-polyoxyalkylene block copolymer. The aqueous lubricant may alsocontain an olefin polymer emulsion.

This application is a continuation of US. Ser. No. 514,104- filed Dec.12, 1965 which is a continuation in part of US. Ser. No. 227,700 filedOct. 2, 1962 and issued as US. Patent No. 3,234,252.

This invention relates to aqueous lubricant compositions containingcertain organosilicon compounds.

Conventional lubricants are generally composed of an organic lubricantbase fluid (e.g. a petroleum oil) to which may have been added one ormore additives (e.g. anti-oxidants and corrosion inhibitors). Suchorganic base fluids are relatively costly and possess poor heat transferproperties which are particularly undesirable when the fluid is employedin a lubricant in operations where a great deal of heat is generated byfriction (e.g. in cutting operations). In such operations the inabilityof the organic base fluid to dissipate the heat may have deleteriouseffects (eg. the fluid may volatilize and/or ignite).

Consequently, efforts have been made to develop lubricants wherein watercomprises part or all of the base fluid since the inexpensiveness, goodheat transfer properties and non-flammability of water obviates many ofthe disadvantages inherent in organic base fluids. The relatively poorload carrying and anti-wear properties of water have been overcome tosome extent in aqueous lubricants by incorporating therein additives.However, prior efforts to develop aqueous lubricants have not beenentirely satisfactory because of the properties of these additives. Forexample, some additives do not impart load carrying or anti-Wearproperties to the lubricant that are adequate for the demands of manyapplications. Other additives are unstable or corrosive. Moreover, someconventional additives impart poor wetting properties to the lubricantor promote foaming and some additives must be employed in excessivelylarge amounts to be effective.

It is an object of this invention to provide additives for aqueouslubricants that impart improved load carrying and anti-wear propertiesto the lubricant, that are relatively stable and non-corrosive, that donot impair the Wetting and anti-foaming properties to the lubricant andthat can be employed effectively in relatively small amounts.

This invention is based on the discovery that copolymers composed of asiloxane moiety linked to a polyoxyalkylene moiety by a silicon tocarbon bond can be em ployed as additives in aqueous lubricantcompositions to achieve the aforementioned objects of this invention. Ithas also been discovered that the performance of the aqueous lubricantcompositions can be further enhanced 3,457,173 Patented July 22, 1969 bythe incorporation therein of a polyolefin in emulsified form.

The lubricant compositions of the present invention comprise an aqueousbase fluid, a siloxane-oxyalkylene copolymer present in an amount in therange fo from about 0.0005 to about 0.1 part by weight, based on onepart by weight of the base fluid. Optionally the compositions can alsocontain, in emulsified form, a polyolefin having molecular weight in therange from about 1,500 to about 25,000, present in an amount in therange from about 0.001 to about 0.1 part by weight per one part byweight of base fluid. When the polyolefin is present in the composition,it is preferred that the weight ratio of the siloXane-oxyalkylenecopolymer to the polyolefin is about 1:1.

The base fluid for the lubricant compositions of this invention can bewater or a water-organic fluid lubricant admixture. The organic fluidlubricant can be 1) a silicon-free polyoxyalkylene compound, (2) adialkyl ester of an aliphatic dicarboxylic acid, (3) a hydrocarbonlubricating oil, (4) an ester of a polyhydric alcohol with a fatty acidor mixtures of the foregoing. Where the base fluid is a Water-organicfluid lubricant admixture, the weight ratio of water to the organicfluid lubricant preferably ranges from about 10:1 to about 1:2,respectively. The weight ratio of water to the organic fluid lubricantin the admixture should not be lower than about 1:2, i.e., the basefluid can contain water and up to about 2 parts by weight of the organicfluid lubricant per one part by weight water.

The siloxane-polyoxyalkylene copolymers that are useful in thecompositions of this invention are of the class that are known as blockcopolymers. Block copolymers are composed of at least two sections orblocks, at least one section or block composed of one type of recurringunits or groups (e.g., siloxane groups as in the copolymers useful inthis invention) and at least one other section or block composed of adifferent type of recurring units or groups (e.g., oxyalkylene groups asin the copolymers useful in this invention). Block copolymers can havelinear, cyclic or branched (crosslinked) structures.

The siloxane blocks in the siloxane-polyoxyalkylene copolymers employedin the compositions of this invention contain at least two siloxanegroups that are represented by the formula:

4-b R Si (I) wherein R is a substituted or unsubstituted monovalenthydrocarbon group or a divalent hydrocarbon group and b has a value from1 to 3 inclusive. Preferably, R contains from one to about thirty carbonatoms. The groups represented by R can be the same or different in anygiven siloxane group or throughout the siloxane block, and the value ofb in the various siloxane groups in the siloxane block can be the sameor different. The divalent hydrocarbon groups represented by R link thesiloxane block to the oxyalkylene block. Each siloxane block contains atleast one group represented by Formula 1 wherein at least one grouprepresented by R is a divalent hydrocarbon group. The siloxane block hasa ratio of hydrocarbon groups to silicon atoms from 1:1 to 3:1.

Illustrative of the unsubstituted monovalent hydrocarbon groups that arepresented by R in Formula 1 are the alkenyl groups (for example, thevinyl and the allyl group); the cycloalkenyl groups (for example, thecyclohexenyl group); the alkyl groups (for example, the methyl, ethyl,isopropyl, octyl and dodecyl groups); the aryl groups (for example, thephenyl and naphthyl groups); the aralkyl groups (for example, the benzyland the phenylethyl groups); the alkaryl groups (for example, thestyryl, tolyl and n-hexylphenyl groups), and the cycloalkyl groups (forexample, the cyclohexyl group). Illustrative of the substitutedmonovalent hydrocarbon groups that are represented by R in Formula 1 arethe alkenyl, cycloalkenyl, alkyl, aryl, aralkyl, alkaryl and cycloalkylgroups having haogeu, cyano, amino, amido, salt, ester, (e.g. carbalkoxyor acyloxy), sulfur-containing (e.g. mercapto, SH) or nitro groups assubstituent-s. Such R groups include the tetrafluoroethyl,trifluorovinyl, chloromethyl, gamma chloropropyl, beta cyanoethyl,gamma-cyanopropyl, cyanophenyl, gamma-amino propyl, delta aminobutyl, Nbetaaaminoethyl-gamma-aminopropyl, aminomethylphenyl, H NCOCH CHbetacarbethoxyethyl, beta-carboxyethyl, MeOOC(CH gammacarbopropoxypropyl, CH COOCH CH CH =CHCOOCH CH beta mercaptoethyl,gamma-mercaptopropyl,

Cl C H SCH CH gamma nitropropyl and nitrophenyl groups. The monovalentsilicon-bonded salt groups include the groups having the formulae:

cHawHmivHwHmoooH-HNwmai (derived from the dibutyl amine salt of oleicacid by reaction with a siloxane containing silanic hydrogen) and(derived from dibutyl tin methacrylate by reaction with a siloxanecontaining silanic hydrogen). Other monovalent silicon-bonded amidegroups include those having the formulae:

C H3 (CHDtH (CH2) BCONMe;

(derived from N,N dimethyl oleamide by reaction with a siloxanecontaining silanic hydrogen) and (derived from N-allyl methylacrylamideby reaction with a siloxane containing silanic hydrogen). Suchsubstituent groups can be used to impart additional desirable propertiesto the copolymers [c.g. increased lubricity (imparted by halogens),self-emulsifying properties (imparted by amide groups), anti-corrosion(imparted by amino groups), increased surface activity (imparted by CN,COOH and ester groups), and higher dielectric properties (imparted by Ngroups)].

Illustrative of the divalent hydrocarbon groups represented by R inFormula 1 are the alkylene groups (such as the methylene, ethylene,propylene, butylene, 2,2 dimethyl 1,3 propylene and decylene groups),the arylene groups (such as the phenylene and p,pdiphenylene groups),the alkarylene groups (such as the phenylethylene group) and thealkylene-aralkylene groups (such as the CH C H CH CH group and the -CH CH CH group). Preferably, the divalent hydrocarbon group is an alkylenegroup containing from two to four successive carbon atoms. Siloxanegroups containing divalent hydrocarbon groups as substituents areillustrated by groups having the formulae:

3 (EH3 -CH2CHzSiOr.5, CH3CHCH2SiO1.5 and --CH2CHzSi0 5" These divalenthydrocarbon groups are linked to a silicon atom of the siloxane block bya silicon-to-carbon bond and to an oxygen atom of the oxyalkylene blockby a carbon-to-oxygen bond.

The siloxane block in the siloxane-polyoxyalkylene copolymers useful inthe compositions of this invention can contain siloxane groups that arerepresented by Formula 1 wherein either the same hydrocarbon groups areattached to the silicon atoms (e.g., the dimethylsiloxy, diphenylsiloxyand diethylsiloxy groups) or different hydrocarbon groups are attachedto the silicon atoms (e.g., the methylphenylsiloxy,phenylethylmethylsiloxy and ethylvinylsiloxy groups).

The siloxane block in the siloxane-polyoxyalkylene copolymers useful inthe compositions of this invention can contain one or more types ofsiloxane groups that are represented by Formula 1 provided that at leastone group has at least one divalent hydrocarbon substituent. By way ofillustration, only ethylenemethylsiloxy groups CH CzH4-Sii0 can bepresent in the siloxane block or the siloxane block can contain morethan one type of siloxane yroup, e.g., the block can contain bothethylenemethylsiloxy groups and diphenylsiloxy groups, or the block cancontain ethylenemethylsiloxy groups, diphenylsiloxy groups anddiethylsiloxy groups.

The siloxane block contained in the siloxane-polyoxyalkylene copolymersuseful in the compositions of this invention can contain tri-functionalsiloxane groups (e.g., mouomethylsiloxane groups, CH SiO difunctionalsiloxane groups [e.g., dimethylsiloxane groups, (CH SiO], monofunctionalsiloxane groups [e.g., trimethylsiloxane groups, (CH SiO or combinationsof these types of siloxane groups having the same or differentsubstituents. Due to the functionality of the siloxane groups, thesiloxane block can be predominantly linear or cyclic or crosslinked orit can have combinations of these structures. When different types ofsiloxane groups, are present they can be alternating, in blocks,randomly distributed or in any other sequence.

The siloxane block contained in the siloxanepolyoxyalkylene copolymersuseful in the compositions of this invention can contain organicend-blocking or chain terminating organic groups, in addition to themonofunotional siloxane chain terminating groups encompassed byFormula 1. By way of illustration, the siloxane block can contain suchorganic end-blocking groups as the hydroxyl group, the aryloxy groups(such as the phenoXy group), the alkoxy groups (such as the methoxy,ethoxy, propoxy and butoxy groups), the acyloxy groups (such as theacetoxy group), and the like.

The siloxane blocks in the siloxane-polyoxyalkylene copolymers useful inthe compositions of this invention contain at least two siloxane groupsthat are represented by Formula 1. Preferably, the siloxane blockscontain a total of from five to twenty siloxane groups that arerepresented by Formula 1. That part of the average molecular weight ofthe copolymer that is attributable to the siloxane blocks can be as highas 50,000 but preferably it is from 220 to 20,000. If that part of theaverage molecular Weight of the copolymer that is attributable to thesiloxane blocks exceeds 50,000 or if the siloxane blocks contain a totalof more than twenty siloxane groups that are represented by Formula. 1,the copolymers are usually difficult to produce.

A siloxane block can contain, in addition to the groups represented byFormula 1, siloxane groups represented by the formula:

wherein R has the meaning defined in Formula 1, e has a value from 0 to2, f has a value from 1 to 2 and (e-H) has a value from 1 to 3,inclusive.

The siloxane block can also contain, in addition to the groupsrepresented by Formula 1, tetrafunctional groups represented by theformula:

wherein R is an unsubstituted monovalent hydrocarbon group as definedfor Formula 1 and n has a value from to 3 inclusive. Illustrative ofsuch groups are the SiO ethoxysiloxy, diethoxysiloxy, triethoxysiloxyand phenoxysiloxy groups.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymersemployed in the compositions of this invention each contain at least twooxyalkylene groups that are represented by the formula:

wherein R is an alkylene group. Preferably, the alkylene grouprepresented by R in Formula 2 contains from two to about ten carbonatoms, and most preferably from two to three carbon atoms. Illustrativeof the oxyalkylene groups that are represented by Formula 2 are theoxyethylene oxy-1,2-propylene, oxy-1,3-propylene, oxy-2,2-dimethyl-1,3-propylene, oxy-1,l0-decylene groups and the like.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymers usefulin the compositions of this invention can contain one or more of thevarious types of oxyalkylene groups represented by Formula 2. By way ofillustration, the oxyalkylene blocks can contain only oxyethylene groupsor only oxypropylene groups or both oxyethylene and oxypropylene groups,or combinations of the various types of oxyalkylene groups representedby Formula 2.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymersemployed in the compositions of this invention can contain organicend-blocking or chain terminating groups. By way of illustration, theoxyalkylene blocks can contain such end-blocking groups as the hydroxygroup, the aryloxy group (such as the phenoxy group), the alkoxy groups(such as the methoxy, ethoxy, propoxy and butoxy groups), alkenyloxygroups (such as the vinyloxy and the allyloxy groups). Also, a singlegroup can serve as an end-blocking group for more than one oxyalkyleneblock. For example, the glyceroxy group,

CHzCllHcHz Ill can serve as an end-blocking group for three oxyalkylenechains.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymers usefulin the compositions of this invention each contain at least twooxyalkylene groups that are represented by Formula 2. Preferably, eachblock contains from two to thirty of such groups. That part of theaverage molecular weight of the copolymer that is attributable to theoxyalkylene blocks can vary from 88 [for (C H O) to 20,000, butpreferably it is from 132 to 15,000. Provided that each oxyalkyleneblock contains at least two oxyalkylene groups represented by Formula 2,the number of oxyalkylene groups and that part of the average molecularweight of the copolymer that is attributable to the oxyalkylene blocksis not critical, but those copolymers in which that part of the averagemolecular weight that is attributable to the oxyalkylene blocks exceeds200,000 or that contain more than fifty oxyalkylene groups per block areless useful, e.g., they are too viscuos for convenient use in theformulations of this invention.

The siloxane-polyoxyalkylene copolymers useful in the compositions ofthis invention can contain siloxane blocks and oxyalkylene blocks in anyrelative amount. In order to possess desirable properties, the copolymershould contain from 5 parts by Weight to 95 parts by weight of siloxaneblocks and from 5 parts by weight to 95 parts by weight of oxyalkyleneblocks per 100 parts by weight of the copolymer. Preferably, thecopolymers contain 5 parts by Weight to 40 parts by weight of thesiloxane blocks and from 60 parts by weight to 95 parts by weight of 2(3) B. Copolymers that contain at least one unit that is represented bythe formula:

Clle l o o siG'o(G"0).G'sio C. Copolymers that contain at least one unitthat is represented by the formula:

In the above Formulas 3, 4 and 5, G is a monovalent hydrocarbon radical,G is a divalent hydrocarbon radical, G" is an alkylene radicalcontaining at least two carbon atoms, G is a hydrogen atom or amonovalent hydrocarbon radical free of aliphatic unsaturation and n hasa value of at least tWo and c has a value from 0 to 2 in Formulas 3 and4 and a value from 0 to 1 in Formula 5. In Formulas 3, 4 and 5, G canrepresent the same different radicals, n preferably has a value from 3to 30 inclusive and G can represent the same or different radicals,i.e., the group (OG) can represent, for example, the groups! -(OC2H4)(OC2H4)(OC3H (OC H (OC H where p and q are integers having a value of atleast one in any given molecule but may have average fractional valuesWhere the formulae represent mixtures of copolymers. Copolymers of thelatter classes can consist only of units represented by Formulae 3, 4 or5 or they can consist of from 1 to 99 mole-percent of such units andfrom 1 to 99 molepercent of units represented by Formula 1 wherein R isan unsubstituted monovalent hydrocarbon group and b has a value from 1to 3 inclusive.

The monovalent hydrocarbon radicals represented by G in Formulas 3, 4and 5 can be saturated or olefinically unsaturated or can containbenzenoid unsaturation. Ilustrative of the monovalent hydrocarbonradicals represented by G are the linear aliphatic radicals (e.g., themethyl, ethyl and decyl radicals), the cycloaliphatic radicals (e.g.,the cyclohexyl and the cyclopentyl radicals), the aryl radicals (e.g.the phenyl, tolyl, Xylyl and naphthyl radicals), the aralkyl radicals(e.g., the benzyl and beta-phenylethyl radicals), and the unsaturatedlinear aliphatic radicals (e.g., the cyclohexenyl radical).

Preferably, the G and G groups [included in the definition of R inFormulas 1 and l-a above] contain from one to about twelve carbon atomsand the G group [included in the definition of R in Formula 2 above]contain from two to about ten carbon atoms. When the G group is amonovalent hydrocarbon radical free of aliphatic unsaturation itpreferably contains from one to about eighteen carbon atoms.

Illustrative of the divalent hydrocarbon radicals represented by G inFormulas 3, 4 and 5 are the alkylene radicals (e.g., the methylene,ethylene, 1,3-propylene, 1,4-butylene and 1,12-dodecylene radicals), thearylene radicals (e.g., the phenylene radical) and the alkaryleneradicals (e.g., the phenylethylene radicals). In Formulas 3, 4 and 5, Gis preferably an alkylene radical containing at least tWo carbon atoms.

Illustrative of the alkylene radicals containing at least two carbonatoms represented by G" in Formulas 3, 4 and 5 are ethylene,1,2-propylene, 1,3-propylene, 1,6- hexylene, 2-ethylheXylene-1,6 and1,12-dodecylene radicals.

Illustrative of the radicals represented by G" in Formulas 3, 4 and 5are the saturated linear or branched chain aliphatic hydrocarbonradicals (e.g., the methyl, ethyl, propyl, n-butyl, tert-butyl and decylradicals), the saturated cycloaliphatic hydrocarbon radicals (e.g., thecyclopentyl and cyclohexyl radicals), the aryl hydrocarbon radicals(e.g., the phenyl, tolyl, naphthyl and xylyl radicals), and the aralkylhydrocarbon radicals (e.g., the benzyl and beta-phenylethyl radicals).

The copolymers employed in the compositions of this invention,particularly those containing at least one unit represented by Formulae3, 4 r 5, can also contain at least one of the units represented by theformulae:

wherein R is an unsubstituted monovalent hydrocarbon group as definedabove, R" is an unsubstituted monovalent hydrocarbon group as definedfor R above, or hydrogen, g has a value from 3 to (or even up to 20)inclusive, It has a value from O to 2 inclusive, i has a value from 2 to3 inclusive, and f has a value from 2 to 4 inclusive. Such copolymerscan contain from 1 to 99 molepercent of units represented by Formulae 3,4 or 5 and from 1 to 99 mole-percent of units represented by Formulae 6,7, 8, 9, 10, 11, or 12. Alternatively such copolymers can contain from 1to 98 mole-percent of units represented by Formulae 3, 4 or 5; from 1 to98 mole-percent of units represented by Formulae 6, 7, 8, 9, 10, 11, or12; and from 1 to 98 mole-percent of units represented by Formula 1wherein R is an unsubstituted monovalent hydrocarbon group and b has avalue from 1 to 3 inelusive.

The organic and inorganic acid salt groups produced from the groupsrepresented by Formulae 6 and 7 and the -COOH groups produced byhydrolyzing the groups represented by Formula 11 can also be present inthe copolymers employed in the compositions of this invention.

The following are representativeof the siloXane-polyoxyalkylene blockcopolymers useful in the compositions of this invention. In theformulas, Me represents methyl (CI-I Bu represents butyl (C H Etrepresents Me (Me LIB SIQ SIO S10 Me SID/I63 COPOLYMER II Me Me MeIVIBaSiO [SID] S10 SIC] MC 5,: I i z SiMe COPOLYMER III Me Me Me MfmsioSIC] SiO SIC] Me 1.7 l 4,1 SiMe;

(CH2)a(O C2 4) "0M6 COPOLYMER IV 13.5 SiMe Me Me MiQaSiO [SID] Me aCOPOLYMER VI C H 0 HzC HzNHCHnCHzNHa MeSiO (MezSiO) 4310 SIMS;

Me CH2CHz(O CzHOsOqS COPOLYMER VII Me C HalHCOOOzHMfi l\!I63SiOSi (M6) 0Si (M02) O 510 HzCHzC Hz O C 4H8 2OII COPOLYMER VIII 0 H: C H; C H C NMe IMeSiOSK O SiMez) AOS IC Hz C Hz (0 (321103 0d:

llile Me COPOLYMER DQ C uHtN O 7; M13 LIQaSiOSi O SIQIB O SI(2)O fi l CH20 H: (O C 2H4)2OM6 ('1 lire COPOLYMER X CHZCHZO 0C CH3 Me LIBSIO Sio SKMez) O 51(4):)0i011z0 HKO 0 3H) 206M COPOLYMER XI OHzCHzGONH: 1H9IVIBBSIOSIOSKMBZ) 0 SK 0 Z) 0 SIICHQC HIGH1( O 0211]): OH

ll le CH2GH2CH2(OC:H4)2OH COPOLYMER XII 1W0 [M (CHaCHzOhCHzC Has ioltCOPOLYMER XIII [45 O (0117CHzOhCHzCHzSiOmh 9 COPOLYMER XIV SIiO M SiMesCOPOLYMER XVI COPOLYMER XVII I Me SiO(MegSiO)z [C iHrKO CrHr) 18.5C3110) 1.10 (CH2)aSli O] SiMea In the examples presented below, thespecific copolymers appearing above are identified for brevity asCopolymer I, Copolymer 11, etc.

The polysiloxane-oxyalkylene block copolymers that are useful in thecompositions of this invention can in general be prepared by twoconvenient methods. The first method, known as the metathesis process,involves forming a mixture of a siloxane polymer containing asiliconbonded, halogen-substituted monovalent hydrocarbon group and analkali metal salt of an oxyalkylene polymer and heating the mixture to atemperature sufliciently elevated (e.g. preferably from 80 C. to 150 C.)to cause the siloxane polymer and the salt to react to produce thecopolymer. This process can be illustrated by the following equation:

I SILOXANE-(OSIiR X) (MO)-OXYALKYI.ENE

SILOXANE- (O SiR O) FOXYALKYLENE rMX wherein R is a divalent hydrocarbongroup, r is an integer that has a value of at least 1 and preferably 1to about 4, X is a halogen atom, M is an alkali metal, SILOXANE denotesa siloxane block and OXYALKYL- ENE denotes an oxyalkylene block.

The second method, known as the addition process, involves forming amixture of an organo-siloxane polymer containing a hydrogen-siloxy group(i.e., a

HSIF

group), an oxyalkylene polymer containing an alkenyloxy end-blocking orchain terminating group and a platinum catalyst (e.g. from 0.001 to 5.0weight-percent based on the reactants of elemental platinum orchloroplatinic acid) and heating the mixture to a temperaturesufficiently elevated (e.g. preferably from 90 C. to 170 C.) to causethe siloxane polymer and the oxyalkylene polymer to react to produce thecopolyrner.

This process can be illustrated by the following equation:

OXYALKYLENE[O RSi 0-], SILOXANE wherein OXYALKYLENE, SILOXANE and r havethe meaning defined for Formula 7, OR is an alkenyloxy group (such asthe vinyloxy and the allyloxy groups) and R is an alkylene groupcontaining at least two successive carbon atoms.

When the polysiloXane-oxyalkylene block copolymer containssilicon-bonded hydrogen atoms, i.e., contains two units represented byFormula 1-a hereinabove, the addition process is preferable. If themetathesis process is used, many of the silicon-bonded hydrogen atomswill undergo side reactions that are catalyzed by the alkali metal ionspresent in the reaction mixture.

When the copolymer useful in this invention contains olefinicallyunsaturated groups attached to silicon (for example, when R in Formulas1 or 1-a above, is alkenyl or cycloalkenyl such as vinyl orcyclohexenyl) it is preferable to prepare these copolymers by additionof the alkenyloxy-end-blocked oxyalkylene polymer to a monomeric,hydrolyzable silane containing silicon-bonded hydrogen, followed byco-hydrolysis or co-condensation with other hydrolyzable silanescontaining silicon-bonded hydrogen and silicon-bonded olefinicallyunsaturated hydrocarbon groups using conventional techniques known tothose versed in the art. For example, reaction of with CH SiHCl in thepresence of a platinum catalyst followed by cohydrolysis of the productwith CH CHSi(CH )Cl CH SiHCl and (CH SiCl gives a copolymer of thisinvention containing units have the formulas [CH O (C H O) CH CH CH Si(CH O] and [CH SiHO], end-blocked with [(CH SiO] groups.

Siloxane-polyoxyal'kylene copolymers containing groups represented byFormulae 6 to 9, 11 and 12 are also readily prepared by additionreactions between copolymers containing groups represented by Formulal-a and suitable olefinically unsaturated organic compounds (e.g.N-allyl ethylene diamine, allyl cyanide, ethyl acrylate, allyl diethylamine, ethyl methacrylate, vinyl acetate, trichlorostyrene and the amideof acrylic acid). In such addition reactions, known catalysts foraddition reactions (e.g. platinum, chloroplatinic acid, amines,phosphines, etc.) can be advantageously employed and the processconditions conventionally employed in known addition reactions areapplicable.

siloxane-polyoxyalkylene copolymers containing groups represented byFormulae 6 to 12 are also readily produced by the cohydrolysis andcocondensation of hydrogen alkoxysilanes [e.g. HSi(OC H andalkoxysilanes containing the appropriate organofunctional groups toproduce a siloxane [e.g. (SiO (O NC H SiO which can then be converted toa siloxane-polyoxyalkylene copolyrner by reaction with a suitablealkenyloxy end-blocked polyoxyalkylene compound in accordance with theabovedescribed addition process. Conventional cohydrolysis andcocondensation procedures can 'be used in this method.

The organic lubricant base fluids that are suitable for use in thevarious compositions of this invention include the various conventionalorganic lubricant base fluids. Typical of suitable lubricants aresilicon-free polyoxyalkyl ene compounds, dialkyl esters of aliphaticdicarboxylic acids, hydrocarbon lubricating oils and esters ofpolyhydric alcohols and fatty acids.

Among the silicon-free polyoxyalkylene compounds that are suitable foruse as organic lubricant base fluids in the compositions of thisinvention are those represented by the formula:

GIH(OGII)nOGIII wherein G'", G" and n have the above-defined meanings.Illustrative of the compounds represented by Formula 1 are 4 9( a s)1o 49 a( s s)12 4 s and C3H1'7(OC3H5)14OC8H17. A preferred class ofcompounds represented by Formula 13 are those having a viscosity between5000 and 12,000 centistokes at -65 F. and a viscosity between 2.5 and3.5 centistokes at 310 F.

Among the dialkyl esters of aliphatic dicarboxylic acids that aresuitable for use as organic lubricant base fluids in the compositions ofthis invention are those represented by the formula:

R"OOC(C H )COOR" wherein R" is an alkyl group containing from 6 tocarbon atoms inclusive and p has a value from 6 to 10 inclusive.Illustrative of the compounds represented by Formula are C H OOC(CH COOCH ethylhexyl)sebacate and C H OOC(CH COOC H Among the hydrocarbonlubricating oils: that are suitable for use as organic lubricant basefluids in the compositions of this invention are the paraffini-clubricating oils, naphthenic lubricating oils and mixtures of such oils.Illustrative of such hydrocarbon lubricating oils are those havingviscosities which range from 30 Saybolt Universal Seconds at 100 F. to100 Saybolt Universal Seconds at 210 F.

Among the esters of polyhydric alcohols and fatty acids that aresuitable for use as organic lubricant base fluids in the compositions ofthis invention are the esters of alcohols such as glycerol,pentaerythritol and trimethylolethane and acids such as olcic acid,stearic acid, coconut fatty acids and Valerie acid. Such esters includethose produced by reacting a polyhdric alcohol with a mixture of fattyacids.

The relative amount of the siloxane-polyoxyalkylene copolymer and thebase fluid employed in the compositions of this invention for bestresults is not narrowly critical and can vary over a wide rangedepending upon such factors as the type of metals to be lubricated bythe composition, the type of organic fluid lubricant, the type ofcopolymer, the temperature and load conditions under which thecomposition is to be used as a lubricant and similar factors. Ingeneral, from about 0.0005 to about 0.1 part by weight of the copolymerper one part by weight of the base fluid (i.e. the water and any organicfluid lubricant) are employed; but from about 0.01 to about 0.05 part byweight of the copolymer per one part by Weight of the base fluid arepreferred. Similarly, the relative amount of Water and any organic fluidlubricant present in the base fluid for best results is not narrowlycritical and it can vary widely depending upon such factors as thecompatibility of the water and the organic fluid lubricant, economicconditions, the compatibility of the copolymer with the base fluid andthe like. In general from 10 to 200 parts by weight of the organic fluidlubricant per 100 parts by weight of Water are desirable but from 50 to130 parts by weight of the organic fluid lubricant per 100 parts byweight of water are preferred. The relative amounts of the copolymer,water and organic fluid lubricant other than those mentioned above canbe employed but no commensurate advantage is gained thereby.

The siloxane-polyoxyalkylene copolymers employed in the compositions ofthis invention can be dissolved in the base fluid to form a solution ordispersed in the base fluid to form an emulsion or a suspension.Similarly, the water and the organic fluid lubricant can be in the formof a solution or an emulsion (i.e. either a water in organic fluidemulsion or an organic fluid in water emulsion).

The polyolefins, when present in an emulsified form, further enhance theproperties of the lubricating compositions of this invention. A suitablepolyolefin is one having molecular weight in the range from about 1,500to about 25,000 and a melting point which preferably does not exceedabout 200 C. Typical of such polyolefins are the homopolymers andcopolymers of an alpha olefin containing from about 2 to about 12 carbonatoms. Because of their emulsifiability, polyoleflns containing on theaverage at least one polar group for every four polyolefin molecules arepreferred.

The polyolefins may be obtained within the aforementioned molecularweight range by direct polymerization, emulsion polymerization, or bythe pyrolysis of a higher molecular Weight polyolefin.

The latter technique is preferred since the pyrolysis of the relativelyhigher molecular weight polymers creates terminal vinyl unsaturationwhich is readily available for reaction with an ethylenicallyunsaturated polar monomer such as maleic anhydride or thioglycolic acid,as taught by US. Patents 2,766,214 and 3,144,348, thereby rendering theresulting polyolefin readily emulsifiable.

Another valuable technique for the preparation of emulsifiable polymershaving a suflicient number of polar groups is by oxidation, with orwithout a catalyst, so as to create pendant carboxylic groups on thepolymer chain along with ketone, aldehyde, and hydroxyl groups. Othersuitable emulsifiable polyoleflns are the block copolymers formed byreacting ethylene oxide with polyethylene so as to produce hydroxylterminated polymers in accordance with the teachings of US. Patent2,921,920. Also suitable polyolefins are the ethylene-alcohol telomersreacted with maleic acid as taught by US. Patent 2,7 66,- 214.

Similarly, the requisite amount of polar groups can be introduced intothe aforementioned homopolymers and copolymers of alpha olefins by thecopolymerization of the resulting polyolefins with unsaturated monomerscontaining the ethylene linkage such as ethylene acrylate, styrene,bicycloheptene, vinyl acetate, acrylic acid, and the like.

In addition, the direct polymerization to and/or hydrolysis of theolefin polymers mentioned above can impart the necessary amount ofpolarity to the polymer chain to make the polymers emulsifiable and theresulting emulsion stable.

Emulsion polymerization is generally carried out by emulsifying theolefin starting material in water by means of a suitable emulsifier andthereafter polymerizing the olefin at elevated pressures andtemperatures in the presence of a polymerization catalyst. Illustrativeemulsion polymerization processes are set forth in US. Patents2,342,400; 2,542,783; 2,592,526; and 2,703,794.

The compositions of this invention can also contain freezing pointdepressants (preferably methanol or ethylene glycol) in an amount from0.01 to about 2 parts by weight (per one part by weight of water in thecomposition). Preferably the freezing point depressant is present in anamount from about 0.01 to about 1 part by weight (per one part by Weightof water in the composition).

In addition, the compositions of this invention can contain, variousother additives so as to impart particular properties to the lubricantcompositions. Among such additives are corrosion inhibitors,anti-oxidants, blooming agents, oiliness agents, anti-wear agents,solubilizers, metal deactivators, extreme pressure additives, viscosityindex improvers, pour point depressants, viscosity moditiers (e.g.glycerol), anti-foam agents, metal dcactivators, wetting agents,adhesive agents, cohesive agents, emulsifying agents, deemulsifyingagents, break-in agents, sludge dispersants, anti-sludge agents,anti-coking agents, detergents, extreme pressure additives and swellingagents (where the composition comes into contact with rubber). Compoundssuch as (MEO OMe can be added as thickeners. The compositions of thisinvention can, if desired, contain the above-mentioned additionaladditives in amounts from about 0.001 to about .05 part by weight (perone part by weight of the base fluid) of each such additive. From about0.005 to about 0.02 part by Weight (per one part by weight of the basefluid) of each such additive are preferred. These additives can beomitted entirely in may applications.

Suitable additional extreme pressure additives include graphite, talc,molybdenum sulfide, alkylamine salts of acid alkyl esters of phosphoricacid in which the amine salt constitutes at least 25 percent by weight,the alkyl groups here referred to containing from 8 to 18 carbon atomseach. Suitable additives coming within this group are dodecylaminedodecyl acid phosphate, blends made up of from 25 to 95 percent ofdodecylamine dodecyl acid phosphate and from 75 to 95 percent of dodecyldihydrogen phosphate, octylamine dioctyl phosphate, di (decylamine)dodecyl phosphate, hexadecylamine dodecyl acid phosphate, octadecylaminedioctadecyl phosphate, and blends containing 2-ethyl-hexylamine,2-ethylhexyl acid phosphate and 2-ethylhexyldihydrogen phosphate inequal proportions. Suitable anti-wear additives include the amine saltsof long chain aliphatic acids, neutral aryl phosphates and neutral alkylaryl phosphates. Representative additives coming Within this groupingare triethanolamine laurate, the dipropylamine, dibutylamine, anddiamylamine salts of lauric acid, triphenyl phosphate, tricresylphosphate, butyl diphenyl phosphate, phenyl dibutyl phosphate, bensyldicresyl phosphate, trixylyl phosphate and diphenyl cresyl phosphate.Suitable metal deactivator additives include quinizarin and alizarin.

The antioxidants that are useful in the compositions of this inventioninclude 1) aromatic compounds that contain at least one substituentgroup that causes the compound to be susceptible to oxidation, (such asan amino, a hydroxyl or an alkoxy group) and (2) dialkyl selenides.

Illustrative of these aromatic antioxidants are such substitutedaromatic compounds as primary, secondary and tertiary aryl amines (forexample, diphenyl amine, n-phenyl-alpha-naphthyl-amine,N-phenyl-beta-naphthylamine and N,N' bis dinaphthyl-para phenylenediamine); hydroxy-substituted aromatic compounds includingalkyl-substituted monohydric phenols (for example2,6di(tert-butyl)4-methyl phenol and G-tert-butylmeta-cresol),aryloxy-substituted phenols (for example 2-(tert-butyl)4-phenoxyphenol), trihydric phenols (for example pyrogallol), dihydric phenols(for example 4- tert-butyl catechol, 4-phenyl catechol,2.5-di(tert-butyl) hydroquinone, 3-methyl catechol and cyclohexylcatechol), di(hydroxyphenol)alkanes [for example bis-(2-hydroxy-3-tert-butyl-5-methyl phenol) methane], dihydric naphthols (forexample, 1,5-dihydroxynaphthylene), hydroxyl-substituted aryl amines(for example ortho-aminophenol, and N-butyl-para-aminophenol) andaralkoxysubstituted phenols (for example hydroquinone monobenzyl ether);and dialkoxy-substituted aromatic compounds (for example, hydroquinonedirnethyl ether). The preferred aromatic antioxidants are thealkyl-substituted monohydric phenols such as 2,6-di(tert-butyl)4- methylphenol and secondary aryl amines, such as N- phenyl-alpha-naphthylamine,N-phenyl beta-naphthylamine and N,N'-bis-dinaphthyl-para-phenylenediamine. In general, it was found that aromatic antioxidants containingamino groups, especially secondary amine groups, were more effective instabilizing the compositions of this invention than aromaticantioxidants containing only hydroxyl groups as substituents.

The dialkyl selenides that are useful in the compositions of thisinvention as anti-oxidants include dihexyl selenide, didodecyl selenide,hexyl dodecyl selenide, di(2- ethylhexyl) selenide, dioctadecylselenide, isooctyl hexadecyl selenide, and the like. In these compoundseach alkyl group attached to the selenium atom preferably contains from6 to 18 carbon atoms.

The corrosion inhibitors that are useful in the compositions of thisinvention include morpholine, the alkali metal nitrites (e.g. potassiumnitrite and sodium nitrite), the alkali metal mercaptobenzothiazoles(e.g. the sodium salt of mercaptobenzothiazole),disalicylalpropylenediamine, amino-organosilicon compounds, alkali metalsalts of carboxyorganosiloxanes, alkenylsuccinic acids, alkeuylsuccinicacid anhydrides, dialkyl acid phosphates, sorbitan mono-oleate, butylstearate, butyl naphthenate and aluminum stearate.

Amino-organosilicon compounds that are useful as corrosion inhibitors inthe compositions of this invention include both the amino-organo(hydrocarbonoxy) silanes and the amino-organosiloxanes wherein theorgano group is a divalent hydrocarbon group containing at least threecarbon atoms and wherein the amino group is connected to silicon throughat least three successive carbon atoms of the organo group. Suitableamino-organo(hydrocarbonoxy)silane corrosion inhibitors includebeta(aminophenyl)ethyltriethoxysilane, gammaaminopropyltriethoxysilane,N (beta aminoethyl)gamma-aminopropyltriethoxysilane andp-aminomethylphenyltriphenoxysilane. Suitable amino-organosiloxanecorrosion inhibitors include homopolymers composed of beta(aminophenyl)ethylsiloxy, gamma aminopropylsiloxy N (betaaminoethyl)gamma aminopropylsiloxy or p-amino-methylphenylsiloxy groupsas well as copolymers composed of one or more of the aforementionedamino-organosiloxy groups and one or more hydrocarbonsiloxy groups (egmethylsiloxy, dimethylsiloxy, trimethylsiloxy and triphenylsiloxygroups).

The alkali metal salts of carboxy-organosiloxanes that are useful ascorrosion inhibitors in the compositions of this invention includealkali metal salts of carboxyalkylsiloxanes wherein the carboxy group islinked to silicon through at least two successive carbon atoms of thealkyl group. Such siloxanes include homopolymers composed ofKOOCCHgCHzSiO KOOCCH CH SiO 5 NaOOCCH CH Si (CH O and LiOOC (CH Si a 5 20.5

groups as well as copolymers composed of one or more of these groups andone or more hydrocarbonsiloxy groups and/or one or more alkali metal-oxysubstituted tetrafunctional siloxy groups [c.g. NaOSiO (NaO) SiO, (NaO)SiO KOSiO and LiOSi0 The alkeuyl succinic acids and anhydrides that areuseful as corrosion inhibitors in the compositions of this invention arethe reaction products of alpha-olefins (e.g. l-octene and l-pentene) andmaleic acid or its anhydride. In these corrosion inhibitors the alkenylgroup preferably contains from 8 to 12 carbon atoms. Illustrative ofthese corrosion inhibitors are octenyl succinic acid and its .anhydrideand pentenyl succinic acid and its anhydride.

The dialkyl acid phosphates that are useful as corrosion inhibitors inthe compositions of this invention preferably contain from 8 to 12carbon atoms in each .alkyl group. Illustrative of such acid phosphatesare dioctyl acid phosphate, didecyl acid phosphate and dilauryl acidphosphate.

The manner in which the compositions of this invention are produced isin no way critical. That is, the components of the compositions can bemixed in any convenient sequence and in any suitable apparatus. Thetechniques applicable to producing conventional aqueous lubricantcompositions can be employed in producing the compositions of thisinvention.

The compositions of this invention are particularly suitable aslubricants for metal, especially as lubricants for ferrous metals, inmetal cutting, forming and machining operations. In addition, thesecompositions are useful as hydraulic fluids, and as mold release agentsfor rubber and plastics. In the latter application, the compositions areapplied to the molds in the usual manner for treating molds withconventional mold release agents.

3,457,173 I 15 re The following test was conducted on compositions ofFor comparison purposes, the results of Falex Wear this invention toevaluate them as lubricants. Tests using copolymer-free (Blank) aqueouslubricant compositions are also shown on Table '11. These blankcompositions are illustrative of conventional aqueous lubricantcompositions.

Falex load and wear test In this test the lubricant is evaluated in aFalex Lubricant Test Machine. The machine consists of a steel shaft Allof the compositions tested contained 1.0 part of and two steel V-blocksthat are positioned so that they morpholine and 1.0 part of potassiumnitrite as corcan be forced against the shaft, The haft and the V-rosion 1nhibitors and 1.0 part of the dibutyl amine salt of blocks areimmersed in the lubricant to be tested. The lauric acid as an additionallubricity-imparting additive. shaft is rotated and a load is applied tothe V-blocks, 10 All parts are parts by Weight.

TABLE II Ethylene Copolymer K Wear Test Glye Polyoxy- Composition Water1 Anti-freeze 1 alkylene 1 2 Type Amount Time (hrs.) Load (lbs.) Wear(mgs) 45.5 32.0 18.4 111 1. 3 200 14 45.5 32.0 13.4 V 1.0 1 1,000 45.532.9 18.4 In 1.0 1 1,000 13 35.0 40.7 18.4 III 1.0 1 1,000 35 45. 32. 91s. 4 None 3 200 22 45. 5 32. 9 1s. 4 None 1 1, 000 175 55. 3 40. 7 0.0 1. 0 1 1, 000 55.3 40.7 0.0 III 1.0 1 1,000 10 55.3 40.7 0.0 III 1.0 12,000 24 50. 0 41. 0 0. 0 None 1 1, 000 32 1 All amounts indicated asparts by weight. 2 Having the average formula: HO(CHgCH O) (C3HO),,H,having a viscosity of 90,000 Saybolt Universal seconds at 100 F. andhaving a weight ratio of -CH2CH2O- to -C3HO- groups of 3:1. forcing themagainst the shaft. The load is increased until 25 EXAMPLE III failureoccurs (i.e. seizure between the rotating shaft and the V-blocks or aradical increase in wear with no increase in load). The load at whichfailure occurs is the Falex Load value for the lubricant. The Falex Loadvalues for various known fluids were determined as Several aqueouslubricant compositions of this invention were tested in the Falex LoadTest at two temperatures. The compositions tested and the testtemperatures are shown in Table III. The parts are parts by weight.

follows: TABLE III Fluid: Falex load (pounds) Copolymer Pam gg g C H (OCH OH 400 Composition yp Parts Water Fluid 1 Temp.,I 4 9( 3 0) 17.7 12501 8 3 r 77 Dimethylpolysiloxane oil 100 1 14 3 A refined petroleum oilhaving a viscosity of 1 30 a 122 about 44 SUS at 210 F. 500 1 99 0.0 Arefined parafiinic hydrocarbon oil having a 5 0 0 97 viscosity of about52 SUS at 210 F. 500 a l 1 5 II 1 99 0 0 The amount of wear wasascertamed by keeping the i 118 load on the V-blOCkS constant (e.g. at200 lbs. 01' 1000 1 A mixture of 2 parts di-2-ethylhexyl sebacate and 1part of a commercially available hydrocarbon lubricating oil that ha aviscosity of f a fixed Perlod of m'zne 1 or 3 hrs) The 44 SayboltUniversal Seconds at 210 F. and has an SAE viscosityof 10W. loss inweight of the rotating shaft caused by contact with the V-blocks is theFalex Wear value for the lubri- Failure seiizllm or P loss of therubbing cant The loss of weight is measured in milligrams D faces bywear d1d not occur 1n any of the tests which were The following examplesillustrate the present inven terminated at a load of 400 pounds in eachof the lower tion: temperature tests and at a load of 800 pounds in eachEXAMPLE I of the h1gher temperature tests. When pure water was tested,excessive wear occurred at a 200' pound load when Several aqueouslubricant compositions of this inventhe test temperature was 86 F. at a250 pound load when tion were produced by simply mixing the indicated cothe test temperature was 250 F. polymers with water or, in one case,with aqueous ethylene glycol. The compositions gave the followingresults EXAMPLE IV on the Falex load test: Copolymer V can be producedby reacting One mole 55 of allyl diethyl amine with one mole of a olymerhaving TABLE I P the formula Amount Failure (30- Load Me Me Me Copolymerpolymer 1 (lbs.) 1

1 0 24 00 fi fi s uOGsHonOH ,0 1.0 3, 200 H M 5.0 1,500 3 E :23 81?, 8The reaction is convemently conducted at a temperature 11 and W 1.0 4,9of 100 C. employing 100 parts per million based on the H and IV fig Qgggweight of reactants of platinum in the form of chloro- 0.7 24,500platinic acid as a catalyst and employing xylene as a i: g 2 it 238Solvent. 4 2 0 li EXAMPLE v l Parts by weight per 100 parts by weight ofwater. No failure to this load at which time the testwas stopped.Copolymer VI can be produced by reacting one mole equa weig mixture H 4equal amounts of water and ethylene glycol used in this run 0 of allylethylene dlamme with one mole of a Polymer having the formula EXAMPLE HH l The Falex Wear Test results with several aqueousMeasiomegsiohsiosmeg lubricant compositions of this invention are shownin Table IL Me CH CHKOCQHQBOxfi 17 The reaction is convenientlyconducted at a temperature of 110 C. employing 100 parts per millionbased on the weight of the reactants of platinum in the form ofchloroplatinic acid as a catalyst and employing toluene as a solventunder reflux conditions.

EXAMPLE VI Copolymer VIII can be produced by reacting one mole of allylcyanide with one mole of a polymer having the formula Me i l Me Si OSIi(OSiMez)iofiiCH CHfloCzHmOo Me Me The reaction is conveniently conductedat a temperature of 125 C. employing two hundred parts per million(based on the weight of the reactants) of platinum in the form ofchloroplatinic acid as a catalyst and employing xylene as a solvent.

EXAMPLE VII Copolymer IX is readily prepared by equilibrating theappropriate methylsiloxanes, nitrophenyl(ethyl)siloxanes andmethylhydrogensiloxanes in the presence of an acid catalyst to produce apolymer having silanic hydrogen and then reacting the latter polymerwith the appropriate vinyl end-blocked oxyalkylene polymer according tothe addition process described hereinabove to produce copolymer IX.Similarly, Copolymers V, VII, VIII, X and XI, as well as othercopolymers having organofunctional substituents, can be produced byanalogous two-step processes involving first the equilibration of theappropriate hydrocarbonsiloxanes, organofunctional siloxanes andhydrogensiloxanes to produce an Si-H containing siloxane which can thenbe reacted by an addition reaction with an alkenyl ether of anoxyalkylene polymer to produce the copolymer.

Copolymers containing organofunctional groups can also be prepared byequilibrating the appropriate hydrocarbonsiloxanes,chlorohydrocarbonsiloxanes and organofunctional siloxanes to produce apolymer that can be reacted through the halohydrocarbon groups thereinwith alkali metal salts of oxyalkylene polymers in accordance with themetathesis procedure described hereinabove.

EXAMPLE VIII Copolymer X can be produced by reacting one mole of vinylacetate with one mole of a polymer having the formula i tMcSiOSliOSKMez) OSi( 2)OSiCHzCH2(O OaHthOMe C2H Me The reaction isconveiently conducted at a temperature of 100 C. employing 50 parts permillion (based on the weight of reactants) of platinum in the form ofchloroplatinic acid as a catalyst and employing toluene as a solvent.

EXAMPLE IX Copolymer XI can be produced by reacting one mole of theamide of acrylic acid with one mole of a polymer having the formula Thereaction is conveniently conducted at a temperature of 200 C. employing250 parts per million (based on the weight of reactants) of platinum inthe form of chlo roplatinic acid as a catalyst.

The evaluation of the following lubricating composttions was carried outusing a Falex Tester where the test equipment comprises a replaceableAt-inch diameter shaft (No. 8 soft steel pin) which is revolved at 290r.p.m. between two steel V-blocks. The shaft can be machined from SAE3135 steel having a Rockwell B hardness of 87 to a 8-10 RMS finish, andthe two V-blocks can be machined from AISI C-1137 steel having aRockwell C hardness of 20 to a 6-8 RMS finish (Method I). In thealternative, the shaft can be machined from M-2 tool steel having aRockwell C hardness of 60 to a 12-14 RMS finish, and the two V-blockscan be machined from 440C stainless steel having a Rockwell C hardnessof 60 to a 12-14 RMS finish (Method II).

The V-blocks are positioned so that they can be forced against the shaftby a notched loading wheel. The adjustment of the loading wheel duringthe test in order to maintain a predetermined load is indicative of thewear on the test shaft. The adjustment of each notch or tooth on theloading wheel indicates 0.000057 inch of wear of the test shaft.

During a test both the shaft and the V-blocks are immersed in thelubricant to be tested.

The operational steps during the test are as follows:

(1) the test is commenced by revolving the shaft between the V-blocksfor 3 minutes at lb. load;

(2) the load is then increased each minute in 100 lb. in-

crements up to 1000 lbs.;

(3) after 1000 lbs. load is reached, further loading is done in 250 lb.increments each minute until seizure of a maximum load of 4500 lbs. isattained;

(4) torque and temperature are recorded each minute;

and

(5) during each one minute interval the wear on the test shaft is notedand recorded as the number of notches on the loading Wheel that have tobe adjusted in order to maintain the desired load.

After the test the average scar width on the V-blocks is measuredmicroscopically and the contact pressure in pounds per square inchcalculated from the following:

gauge load seizure F2 bearing load, lbs. scar length, in. scar width,in.

=bearing load, lbs.

pounds per sq. inch scar length=0.5 inch EXAMPLE X sented in Table IVbelow.

TABLE IV Identification of Seizure Emulsifier Emulsion Type of Emulsionload, lbs. Type Carboxylated SBR 3,000

. Polyethylene 4,500 Nonionio.

0.2 wt. percent; Copolymer 1, 250

XVIII control.

The foregoing data indicate that the combination of an aqueouspolyolefin emulsion with a siloXane-oxyalkylene copolymer provides alubricating composition having very good load carrying and anti-weldproperties.

EXAMPLE XI The effect of the addition of a siloxane-oxyalkylenecopolymer to an aqueous polyolefin emulsion on contact pressures wasdetermined in a Falex Tester employing Method II. The test results arereported in Table V below.

TABLE V Gage Avg Lubricant Tested 111 Water Load, Scar ContactContaining 0.1 wt. percent lbs, at Width, lrcssure, Gopolymer XVIIISeizure inches p.s.i.

0.1 wt. percent Additional Oopolymer XVIII l, 250 049 40, 000 0.1 wt.percent Emulsion F solids- 3,250 016 200,000 0.1wt. percent Emulsion Asolids 4, 500 016 400, 000 D 4, 000 014 400, 000 0.1 wt. percentEmulsion I solids 2, 750 021 100, 000 0.1 wt. percent triethanolaniineluuratc (soap) 2, 500 012 300, 000

Proof of synergism0omparo with above 0.2 wt. percent Emulsion F solids2, 500 015 240, 000 0.2 wt. percent Emulsion A solids 3, 000 016 260,000 0.2 wt. percent Copolymer XVIII... l, 250 040 40, 000

Characterization of the above emulsions Emulsion A.-An aqueous,non-ionic emulsion of chemically inert, low molecular weightpolyethylene emulsified by a polyoxyethylene derivative of an aliphaticcompound.

Emulsion F.An aqueous, non-ionic emulsion of cracked, high-densitypolyethylene (molecular weight: about 2000) modified with about weightpercent maleic anhydride and emulsified with a mixture of nonylphenylpolyethylene glycol ethers containing about 4 and about 7 moles ofethylene oxide and with morpholine.

Emulsion I.An aqueous, non-ionic emulsion of lowdensity, polyethylene(molecular weight: about 24,000) prepared by emulsion polymerization.

Emulsion P.An aqueous styrene-butadiene latex.

The foregoing data demonstrate that a synergetic increase in contactpressures can be obtained by the combination of a siloxane-oxyalkylenecopolymer with a polyolefin in an aqueous emulsion.

Concentrated admixtures containing an above-described base fluid andrelatively large amounts of the above-described siloxane-polyoxyalkylenecopolymers can be conveniently and economically stored and shipped. Suchadmixtures can then be readily diluted just prior to use to produce theaqueous lubricant compositions of this invention described above. Theconcentrated admixtures can contain from over 0.1 part up to 0.5 or evenas high as 0.7 part by weight of the copolymer per one part by weight ofthe base fluid. These admixtures can also contain the various additionaladditives described above in amounts from over 0.5 part to up to 0.25 oreven as high as 0.35 part by Weight per one part by weight of the basefluid. Dilution of such admixtures to form aqueous lubricantcompositions of this invention is readily accomplished by mixing theadmixtures with water or with mixtures of water and an organic lubricantbase fluid.

It should be understood that the various above-mentioned additionaladditives which may be present in the aqueous lubricant composition ofthis invention are not an exhaustive list of such materials. By way ofillustration, a base (e.g. sodium hydroxide) can be added to thecomposition of this invention when necessary or desirable in order tomaintain the pH of the composition above 7. As a further illustration,anti-microbacterial agents such as an aqueous solution containingdi(phenyl mercuric) ammonium propionate in an amount providing about 6wt. percent of mercury can be added to the compositions of thisinvention. Other bactericidal agents that can be employed are thechlorophenols, the neornycin sulfates, 6-acetoxy-2,4-dimethyl-n-dioxane,and the like. As a further illustration, silicone anti-foam agents canbe added to the composition. Illustrative of the suitable types ofsilicone anti-foam agents are trimethylsiloxy-endblockeddimethylpolysiloxane oils having a viscosity from 350 to 500 centistokesat 25 C. Such oils can be mixed with finely divided silica, e.g. about 3wt. percent silica.

The foregoing discussion and the examples are intended as illustrativeof the present invention. Other variations and modifications within thespirit and scope of this invention will readily present themselves tothe skilled artisan.

What is claimed is:

1. A method for lubricating two metal surfaces in moveable contact witheach other which method comprises applying to the surfaces a compositioncomprising an aqueous base fluid and from about 0.0005 to about 0.1 partby weight per one part by weight base fluid of a siloxane-oxyalkylenecopolymer having:

(a) at least one siloxane block containing at least two siloxane groupsrepresented by the formula:

Rbsl O2 wherein R is a member of the group consisting of a monovalenthydrocarbon group, halosubstituted monovalent hydrocarbon group,cyano-substituted monovalent hydrocarbon group, amino-substitutedmonovalent hydrocarbon group, carbalkoxy-substituted monovalenthydrocarbon group, acyloxy-substituted monovalent hydrocarbon group,mercapto-substituted monovalent hydrocarbon group, nitro-substitutedmonovalent hydrocarbon group, and a divalent hydrocarbon group, and bhas a value from 1 to 3, inclusive, and the siloxane block has at leastone divalent hydrocarbon group represented by R; and

(b) at least one polyoxyalkylene block containing at least twooxyalkylene groups represented by the formula:

wherein R is an alkylene group, each siloxane block being linked to eachpolyoxyalkylene block by the divalent hydrocarbon group represented byR; said aqueous base fluid containing water and up to about 2 parts byweight per one part by weight Water of an organic fluid lubricant whichis a member of the group consisting of a silicon-free polyoxyalkylenecompound, a dialkyl ester of an aliphatic dicarboxylic acid, ahydrocarbon lubricating oil, and an ester of polyhydric alcohol with afatty acid.

2. The method of claim 1 wherein the compositions also contain an olefinpolymer in emulsified form having an average molecular weight from about1,500 to about 25,000 and being present in an amount in the range fromabout 0.001 to about 0.1 part by weight per one part by weight of thebase fluid.

3. The method of claim 2 wherein the base fluid is water.

4. The method of claim 1 wherein the siloxane polyoxyalkylene blockcopolymer is present in an amount from about 0.001 to about 0.05 part byWeight per one part by weight of the base fluid.

5. The method of claim 1 wherein R is a monovalent hydrocarbon group ora divalent hydrocarbon group.

6. A lubricant composition comprising:

(A) an aqueous base fluid containing Water and up to about 2 parts byweight per one part by weight water of an organic fluid lubricant whichis a member of the group consisting of a silicon-free polyoxyalkylenecompound, a dialkyl ester of an aliphatic dicarboxylic acid, ahydrocarbon lubricating oil and an ester of polyhydric alcohol with afatty acid;

(B) from about 0.0005 to about 0.1 part by weight per one part by weightbase fluid of a siloxaneoxyalkylene copolymer having:

(a) at least one siloxane block containing at least two siloxane groupsrepresented by the formula;

RbSiO wherein R is a member of the group consisting of a monovalenthydrocarbon group, halo-substituted monovalent hydrocarbon group,cyanosubstituted monovalent hydrocarbon group, aminosubstitutedmonovalent hydrocarbon group, amide-substituted monovalent hydrocarbongroup, carbalkoxy-substituted monovalent hydrocarbon group,acyloxy-substituted monovalent hydrocarbon group, mercapto-substitutedmonovalent hydrocarbon group, nitro-substituted monovalent hydrocarbongroup, and a divalent hydrocarbon group, and b has a value from 1 to 3,inclusive, and the siloxane block has at least one divalent hydrocarbongroup represented by R; and

(b) at least one polyoxyalkylene block containing at least twooxyalkylene groups represented by the formula:

wherein R is an alkylene group, each siloxane block being linked to apolyoxyalkylene block by the divalent hydrocarbon group represented byR, and

(C) an olefin polymer in emulsified form having an average molecularweight in the range from about 1,500 to about 25,000 and being presentin an amount in the range from about 0.001 to about 0.1 part by weightper one part by weight of the base fluid.

7. The composition of claim 6 wherein the siloxanepolyoxyalkylene blockcopolymer is present in an amount of from about 0.001 to about 0.05 partby weight per one part by weight of the base fluid and wherein R is amonovalent hydrocarbon group or a divalent hydrocarbon group. i

8. A composition as defined in claim 6 consisting essentially of (A)water, (B) from about 0.001 to about 0.1 part by weight per one part byweight water of an olefin polymer in emulsified form having an averagemolecular weight in the range of from about 1,500 to about 25,000, and(C) from about 0.0005 to about 0.1 part by weight per one part by weightwater of a siloxane-polyoxyalkylene copolymer as defined in claim 6wherein R is a monovalent hydrocarbon group or a divalent hydrocarbongroup.

9. The composition of claim 8 wherein the olefin polymer contains on theaverage of at least one polar group for every four olefin polymermolecules.

10. An admixture consisting essentially of:

(A) an aqueous base fluid containing water and up to about 2 parts byweight per one part by weight water of an organic fluid lubricant whichis a member of the group consisting of a silicon-free polyoxyalkylenecompound, a dialkyl ester of an aliphatic dicarboxylic acid, ahydrocarbon lubricating oil, and an ester of polyhydric alcohol with afatty acid;

(B) a siloxane-oxyalkylene block copolymer having:

(a) at least one siloxane block containing at least two siloxane groupsrepresented by the formula:

RbSiO wherein R is a member of the group consisting of a monovalenthydrocarbon group, halo-substituted monovalent hydrocarbon group,cyanosubstituted monovalent hydrocarbon group, amino-substitutedmonovalent hydrocarbon group, amide-substituted monovalent hydrocarbongroup, carbalkoxy-substituted monovalent hydrocarbon group,acyloxy-substituted monovalent hydrocarbon group, mercapto-substitutedmonovalent hydrocarbon group, nitro-substituted monovalent hydrocarbongroup and a divalent hydrocarbon group, and b has a value from 1 to 3,inclusive, and the siloxane block has at least one divalent hydrocarbongroup represented by R; and

(b) at least one polyoxyalkylene block containing at least twooxyalkylene groups represented by the formula:

wherein R is an alkylene group, each siloxane block being linked to apolyoxyalkylene block by the divalent hydrocarbon group represented by Rin an amount from over 0.1 to 0.7 part by weight per part by weight ofthe aqueous base fluid, and

(C) an olefin polymer having an average molecular weight in the rangefrom about 1,500 to about 25,000 in an amount from over 0.05 part up to0.35 part 1l ly weight per part by weight of the aqueous base 11. Anadmixture as defined in claim 10 consisting essentially of:

(A) water,

(B) a siloxane-oxyalkylene block copolymer as defined in claim 10wherein R is a monovalent hydrocarbon group or a divalent hydrocarbongroup, said block copolymer being present in an amount from over 0.1 to0.7 part by weight per part by weight of the water, and

(C) an ethylene polymer having an average molecular weight in the rangefrom about 1,500 to about 25,000 in an amount from over 0.05 part up to0.35 part by weight per part by weight of the water.

12. The admixture of claim 11 wherein the ethylene polymer contains onthe average of at least one polar group for every four ethylene polymermolecules.

References Cited UNITED STATES PATENTS 3,234,252 2/1966 Pater 252-493 X3,256,211 6/1966 Bailey et al 252-493 X 3,280,160 10/1966 Bailey260-4482 3,299,112 1/1967 Bailey 260-4482 2,122,826 7/1938 Van Peski252-55 2,142,980 1/1939 Huijser et a1 2 2-5 2,561,178 7/1951 Burkhard252-496 2,846,458 8/1958 Haluska 252-496 2,868,824 1/1959 Haluska252-496 2,941,944 6/1960 Ervine 252-495 2,965,596 12/1960 Sharf 260-2963,198,820 8/1965 Pines et al. 260-448.2

FOREIGN PATENTS 718,179 11/1954 Great Britain. 785,780 11/1957 GreatBritain.

DANIEL E. WYMAN, Primary Examiner W. CANNON, Assistant Examiner US. Cl.X.R.

